KR19990070970A - Method for producing porous polymer particles - Google Patents
Method for producing porous polymer particles Download PDFInfo
- Publication number
- KR19990070970A KR19990070970A KR1019980006154A KR19980006154A KR19990070970A KR 19990070970 A KR19990070970 A KR 19990070970A KR 1019980006154 A KR1019980006154 A KR 1019980006154A KR 19980006154 A KR19980006154 A KR 19980006154A KR 19990070970 A KR19990070970 A KR 19990070970A
- Authority
- KR
- South Korea
- Prior art keywords
- acrylate
- methacrylate
- monomer
- particle size
- polymer particles
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 149
- 229920000642 polymer Polymers 0.000 title claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 78
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- -1 seeds Substances 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 230000008961 swelling Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 4
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 description 24
- 238000009826 distribution Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 229920002223 polystyrene Polymers 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000012674 dispersion polymerization Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 6
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 238000012673 precipitation polymerization Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VXJOXUWCOXCVFK-UHFFFAOYSA-N tetrachloromethane;toluene Chemical compound ClC(Cl)(Cl)Cl.CC1=CC=CC=C1 VXJOXUWCOXCVFK-UHFFFAOYSA-N 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
본 발명은 다공성 중합체 입자의 제조 방법에 관한 것이다.The present invention relates to a process for producing porous polymer particles.
본 발명은 소수 및 친수성의 모노비닐 단량체 , 분산안정제, 유상의 개시제, 가교제로서 디비닐 단량체, 희석제, 증류수 및 시이드 중합체 등의 매개물을 초음파 발생장치를 사용하여 상기 용액 속에 균일하게 분산시켜 혼합하는 단계, 분산안정제에 의하여 용액 속에 균일하게 분산되어 있는 시이드 중합체를 희석제와 단량체에 의하여 일정한 크기로 팽윤시켜, 팽윤된 시이드 속으로 상기 매개물들을 녹이는 단계, 상기 용액을 반응이 일어날 수 있는 온도로 가열하여 중합반응을 일으키는 단계, 및 중합반응이 완결되고 미반응 단량체, 시이드, 희석제 및 분산안정제 등을 제거하기 위하여 유기용매와 물을 사용하여 세척하는 단계로 이루어진 입자크기가 균일한 다공성 중합체 입자의 제조방법이다.The present invention is to uniformly disperse and mix the media such as divinyl monomers, diluents, distilled water and seed polymers as hydrophobic and hydrophilic monovinyl monomers, dispersion stabilizers, oil phase initiators, crosslinking agents in the solution using an ultrasonic wave generator. Swelling the seed polymer uniformly dispersed in the solution by a dispersion stabilizer to a predetermined size with a diluent and a monomer to dissolve the media into the swelled seed, and bringing the solution to a temperature at which the reaction can occur. A porous polymer particle having a uniform particle size consisting of heating to cause a polymerization reaction and washing with an organic solvent and water to complete the polymerization reaction and to remove unreacted monomers, seeds, diluents and dispersion stabilizers. It is a manufacturing method of.
이와 같은 제조방법으로 입자의 크기가 정확히 조절되고, 입자의 크기가 균일한 다공구조를 갖는 중합체 입자를 제조할 수 있다.By the production method as described above, the size of the particles can be precisely controlled and polymer particles having a uniform porous structure can be produced.
Description
본 발명은 다공성 중합체 입자의 제조방법에 관한 것이다. 더욱 상세하게는 입자 크기가 정확히 조절되고, 입자 크기가 균일한 다공성 중합체 입자를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing porous polymer particles. More particularly, the present invention relates to a method for producing porous polymer particles having precisely controlled particle sizes and uniform particle sizes.
일반적으로 입자의 형태가 구형인 중합체는 비표면적이 넓기 때문에 효소 고정화제 또는 촉매 담체 등으로 응용할 때 충분한 반응장소를 제공할 수 있으며, 저점도 특성으로 다루기가 쉽고, 치환기 도입에 의한 기능화가 비교적 용이하기 때문에 중합체 입자의 물리, 화학적인 특성에 따라 여러 분야에 응용되고 있다.In general, polymers having a spherical morphology have a large specific surface area and thus can provide a sufficient reaction site when applied as an enzyme immobilizing agent or a catalyst carrier, and are easy to handle with low viscosity and relatively easy to functionalize by introducing a substituent. Therefore, it is applied to various fields according to the physical and chemical properties of polymer particles.
또한, 구형의 중합체는 입자가 수 ㎛ 내지 수십 ㎛의 입자크기를 갖고 입도분포가 단분산성이면 전자사진용 토너, 액정 디스플레이 패널용 캡-조절제, 쿨터카운터의 표준입자 및 화장품의 첨가제 등으로 사용될 수 있다.In addition, the spherical polymer may be used as an electrophotographic toner, a cap-controller for liquid crystal display panels, standard particles of a cooler counter and additives for cosmetics if the particles have a particle size of several micrometers to several tens of micrometers and the particle size distribution is monodisperse. have.
특히, 입자의 형태가 구형이며 크기가 균일하고 입자표면에 다공구조를 갖는 중합체는 칼럼 충진제, 단백질의 흡착 분리용 담체, 중금속 및 이온성 물질을 흡착 분리하는 킬레이트수지 등에 응용성을 갖고 있다.In particular, polymers having a spherical morphology, uniform size, and porous structure on the particle surface have applications such as column fillers, carriers for adsorptive separation of proteins, and chelate resins for adsorptive separation of heavy metals and ionic materials.
이러한 중합체에 대한 연구는 초기에 폴리스티렌과 같이 비교적 단단하고 화학적으로 안정한 특성을 가지고 있는 물질에 대하여 진행되어 왔으며, 특히 분리능이 우수하며 내구성, 내압성이 좋은 중합체를 합성하기 위해서는 중합체 입자의 다공도, 입자크기 및 입도분포를 적절히 조절할 수 있어야 한다는 필요성이 있다.Research into such polymers has been conducted in the early days for materials having relatively hard and chemically stable properties such as polystyrene, and in order to synthesize polymers having excellent separation ability and durability and pressure resistance, polymer porosity and particle size And there is a need to be able to adjust the particle size distribution properly.
칼럼 충진제로 사용되고 있는 중합체 물질은 스티렌-디비닐벤젠 공중합체와 같은 소수성 중합체과 아크릴아미드-메틸렌비스아크릴아미드 공중합체와 같은 친수성 중합체 등 여러 종류가 상품화되어 있다. 그러나 국내에서는 아직까지 분리용 중합체 물질 합성기술에 영향을 주는 단량체, 희석제, 안정제의 선택, 반응온도 및 교반속도 등 중합공정 기술이 제대로 확립되지 못하였기 때문에 외국에서 이를 수입하여 사용하고 있다.Polymeric materials used as column fillers are commercially available, including hydrophobic polymers such as styrene-divinylbenzene copolymers and hydrophilic polymers such as acrylamide-methylenebisacrylamide copolymers. However, in Korea, the polymerization process technology such as monomer, diluent, stabilizer selection, reaction temperature and agitation rate, etc. affecting the polymer material synthesis technology has not yet been properly established and imported from abroad.
따라서 분리능이 우수하고 내구성, 내약품성이 우수한 칼럼 충진제와 흡착분리용 중합체를 개발하기 위한 연구가 요구되고 있으며, 최근에는 중금속에 의한 수질 및 환경오염 문제가 심각하게 대두되고 있기 때문에 여러 분야에서 금속이온을 선택적으로 분리할 수 있는 금속 킬레이트 수지에 대한 관심 또한 높아지고 있다.Therefore, research to develop column fillers and polymers for adsorptive separation, which have excellent separation ability, durability and chemical resistance, is required. In recent years, water quality and environmental pollution problems caused by heavy metals have emerged seriously. There is also increasing interest in metal chelate resins that can selectively separate.
일반적으로, 중합체는 유화중합, 현탁중합, 분산중합, 침전중합 및 시이드중합 등으로 제조할 수 있는데, 각각의 중합법에 따라 얻어지는 중합체는 입자크기, 입도분포 및 분자량 등 물리적인 특성이 다르다.In general, the polymer can be prepared by emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization and seed polymerization, and the polymer obtained by each polymerization method has different physical properties such as particle size, particle size distribution and molecular weight.
유화중합은 일반적으로 용매(물), 수용성 개시제 및 유화제 등을 사용하여 용액 속에서 친수성/소수성 부분을 가지고 있는 미셀을 형성하고 용매에 불용인 단량체가 미셀의 소수성 부분으로 녹아 들어가 중합이 이루어진다. 이 때 얻어진 중합체는 높은 중합도의 단분산성 미세입자가 만들어지는 반면에 분자량 분포가 넓다. 입자크기는 유화제와 개시제의 농도에 의하여 어느 정도 조절할 수 있지만 보통 1㎛ 이하의 작은 입자들이 얻어진다. 또한 반응 후 중합체에 포함되어 있는 유화제의 제거가 어렵고 유화제를 사용하지 않은 유화중합법으로 중합체 입자를 합성할 때는 조금 큰 입자를 얻을 수는 있지만 입도분포가 넓어지는 단점이 있다.Emulsion polymerization generally uses a solvent (water), a water-soluble initiator, and an emulsifier to form a micelle having a hydrophilic / hydrophobic portion in a solution, and monomers insoluble in the solvent are dissolved into the hydrophobic portion of the micelle to perform polymerization. The polymer obtained at this time produces a high degree of polymerization of monodisperse microparticles, while having a wide molecular weight distribution. The particle size can be controlled to some extent by the concentration of the emulsifier and the initiator, but small particles of 1 μm or less are usually obtained. In addition, it is difficult to remove the emulsifier contained in the polymer after the reaction, and when the polymer particles are synthesized by the emulsion polymerization method without using the emulsifier, slightly larger particles can be obtained, but the particle size distribution has a disadvantage.
현탁중합은 보통 용매로서 물을 사용하고 용매에 잘 녹지 않는 단량체와 개시제를 첨가하여 격렬하게 교반시키면 개시제가 단량체 속으로 녹아 들어가 작은 비말(droplet)의 형태로 용매 속에 분산된다. 중합은 단량체 비말 속에서 이루어지고 형성된 중합체는 용매 속에서 녹지 않고 입자로 얻어진다.Suspension polymerization usually uses water as a solvent and vigorously stirs the monomer and the initiator which are insoluble in the solvent. The initiator melts into the monomer and is dispersed in the solvent in the form of small droplets. The polymerization takes place in monomer droplets and the resulting polymer is obtained as particles without melting in a solvent.
그러나 용매에 가용성인 개시제를 사용하면 중합은 단량체 비말과 용매의 계면(비말과의 표면)에서 이루어지는데 이를 분산중합이라고 한다. 또한 단량체 비말의 병합을 막고 현탁이나 분산을 균일하고 안정하게 하기 위하여 젤라틴, 녹말, 에틸셀룰로오스, 폴리비닐알콜 등을 분산안정제로 사용한다.However, when an soluble initiator is used in the solvent, the polymerization takes place at the interface between the monomer droplet and the solvent (surface of the droplet), which is called dispersion polymerization. In addition, gelatin, starch, ethyl cellulose, polyvinyl alcohol, and the like are used as dispersion stabilizers to prevent incorporation of monomer droplets and to make suspension and dispersion uniform and stable.
현탁중합으로 입자표면에 세공이 발달된 다공구조의 형성은 반응시스템 속에서 중합이 진행되는 동안 형성된 공중합체들의 상분리에 의하여 일어나므로 중합시스템에 사용된 희석제의 선택은 얻어진 중합체 입자의 세공구조를 결정하는데 중요한 인자로 작용한다.Suspension polymerization results in the formation of a porous structure in which pores are developed on the particle surface by phase separation of copolymers formed during polymerization in the reaction system. Therefore, the selection of the diluent used in the polymerization system determines the pore structure of the obtained polymer particles. It is an important factor.
분산중합은 단량체, 개시제 및 분산안정제 등이 출발 매개물 속에서 반응하는 동안 중합체 입자들이 용매상에 침전되는데, 사용된 단량체 및 분산안정제와 결합하는데 있어서 사용될 수 있는 용매들이 선택적으로 요구된다. 그러나 반응이 진행되면서 중합체 입자들이 핵으로 되고 개시제와 단량체가 용매와 중합체상 사이에서 분배되는 것으로 각각의 상에서 관련된 매개물질의 첨가량은 용매, 반응온도 및 다른 여러 인자들의 선택에 의하여 결정된다.Dispersion polymerization requires that polymer particles precipitate on the solvent while monomers, initiators, and stabilizers react in the starting medium, optionally requiring solvents that can be used to bind the monomers and dispersion stabilizers used. However, as the reaction proceeds, the polymer particles are nucleated and the initiator and monomer are partitioned between the solvent and the polymer phase. The amount of the mediator involved in each phase is determined by the choice of solvent, reaction temperature and several other factors.
중합의 초기 단계에서 생성되는 초기의 집합체들이 형성되는 핵의 수를 결정하므로 중합체의 형성은 반응초기에 생성되는 집합체의 수에 의존한다. 형성된 핵들은 사용된 단량체의 양에 따라 연속적으로 입자의 크기가 커진 구형입자로 성장되고, 마지막 입자크기와 입도분포는 주로 사용된 단량체의 양과 성장하는 입자들의 콜로이드성 안정성을 유지하기 위하여 첨가된 분산안정제의 역할에 의하여 결정된다.The formation of the polymer depends on the number of aggregates produced at the beginning of the reaction since the initial aggregates produced at the initial stage of polymerization determine the number of nuclei formed. The nuclei formed are subsequently grown into spherical particles of larger particle size depending on the amount of monomer used, and the final particle size and particle size distribution are mainly added to maintain the amount of monomer used and colloidal stability of the growing particles. Determined by the role of stabilizers.
현탁 및 분산중합에서 입자의 크기 조절은 열역학적 또는 동력학적인 인자들의 함수로서 (1)단량체-중합체의 용해력 (2)반응물의 조성 (3)반응온도 (4)용매 매개물 등에 의존하게 된다. 반응온도는 생성되는 중합체의 분자량, 중합속도 및 입자핵을 결정하는 개시제의 분해속도 뿐만아니라 용해도 등 열역학적인 인자들에 영향을 준다.The particle size control in suspension and dispersion polymerization depends on (1) the solubility of the monomer-polymer (2) the composition of the reactants (3) the reaction temperature (4) the solvent media, etc. as a function of thermodynamic or kinematic factors. The reaction temperature affects thermodynamic factors such as solubility as well as the rate of decomposition of the initiator that determines the molecular weight, polymerization rate, and particle nucleus of the resulting polymer.
단량체가 용매계의 일부분이고 매개물 속에서 단량체의 농도는 중합이 일어날 때 일정하게 감소되므로 단량체가 중합공정에서 차지하는 역할은 용매의 역할보다 더 중요하다. 그러나 용매계 속에서 이러한 매개물들의 역할은 상호관계에 있어서 매우 복잡하다. 중합 초기단계에서 입체적으로 안정화된 ㎛ 크기의 작은 비말 속으로 단량체상들이 물리적으로 분해되어 들어가고 뒤따라 라디칼 개시에 의하여 중합되기 때문에 넓은 입도분포를 나타낸다.Since the monomer is part of the solvent system and the concentration of monomer in the medium is constantly reduced when polymerization takes place, the role of monomer in the polymerization process is more important than the role of solvent. However, the role of these mediators in the solvent system is very complicated in their interrelationships. In the early stages of polymerization, the monomer phases are physically decomposed into small, three-dimensionally stabilized droplets of micrometer size, and thus have a wide particle size distribution because they are polymerized by radical initiation.
이와 같은 현탁중합 및 분산중합으로는 중합체의 분자량을 제어할 수 없고, 입자크기 및 사용되는 단량체가 한정적이라는 단점이 있다.Such suspension polymerization and dispersion polymerization can not control the molecular weight of the polymer, there is a disadvantage that the particle size and the monomer used are limited.
침전중합법은 단량체와 개시제를 녹이는 균일상 용액 중에서 유화제나 분산안정제를 사용하지 않는 중합법으로 생성된 중합체가 용매에 녹지 않고 중합 후 석출되는 중합법이다. 미크론(㎛) 크기의 입자를 얻을 수 있지만 입도분포가 넓으며 중합체가 합성되면서 대개의 경우 작은 입자로 얻어지기 보다는 큰 집합체나 덩어리 형태가 생기기 쉽다. 또한 좁은 분자량 분포의 중합체를 얻을 수 있으나 고분자량의 입자를 얻기가 어렵다.Precipitation polymerization method is a polymerization method in which a polymer produced by a polymerization method without using an emulsifier or a dispersion stabilizer is precipitated after polymerization without dissolving in a solvent in a homogeneous solution in which monomers and an initiator are dissolved. Micron (μm) sized particles can be obtained, but the particle size distribution is wide, and as polymers are synthesized, large aggregates or agglomerates are more likely to occur than large particles. In addition, polymers of narrow molecular weight distribution can be obtained, but high molecular weight particles are difficult to obtain.
영국 폴리머 저널(Brit. Polym. J., 14, 131, 1982)에 알코올을 용매로 하고 4차 암모늄염을 분산제로 사용한 분산중합법으로 1㎛ 내지 6㎛ 크기를 갖는 비교적 균일한 중합체 입자의 제조방법에 대하여 기술되었다.A method for producing relatively uniform polymer particles having a size of 1 to 6 µm by a dispersion polymerization method using alcohol as a solvent and quaternary ammonium salt as a dispersant in the British Polymer Journal (Brit. Polym. J., 14, 131, 1982). Has been described.
또한, 저널 오브 폴리머 사이언스 폴리머 레터(J.Polym. Sci. Polym. Lett. Ed., 23, 103, 1985)에는 여러 가지 용매 속에 분산안정제로 비이온성 셀룰로오스 유도체를 사용하여 수 ㎛ 크기를 갖는 폴리스티렌 입자의 제조방법에 대하여 기술되었다.In addition, the Journal of Polymer Science Polymer Letter (J.Polym. Sci. Polym. Lett. Ed., 23, 103, 1985) has a polystyrene particle having a size of several micrometers using nonionic cellulose derivatives as a dispersion stabilizer in various solvents. It was described with respect to the manufacturing method of.
한편, 대한민국 특허 95-10230(KR)에는 미세 입자의 단분산성 중합체 겔을 얻기 위하여 일차적으로 합성한 가교중합체를 용매 속에 팽윤시키고 제한된 공간내에 이차적으로 단량체를 혼입시키는 새로운 침전중합법이 기술되었다.On the other hand, Korean Patent 95-10230 (KR) has described a new precipitation polymerization method to swell the first synthesized cross-linked polymer in a solvent in order to obtain a monodisperse polymer gel of fine particles and to incorporate the monomer secondary in a limited space.
그러나, 상기와 같은 유화중합, 현탁중합, 분산중합 및 침전중합법 등으로는 수 ㎛에서 수십 ㎛ 이상의 크기를 갖는 구형의 중합체 입자를 얻을 수 있으나, 분자량을 제어하는 것이 불가능하며 분자량 분포가 넓고 사용 가능한 용매와 단량체가 한정적이라는 문제점이 있다.However, spherical polymer particles having a size of several micrometers to several tens of micrometers or more can be obtained by the emulsion polymerization, suspension polymerization, dispersion polymerization, and precipitation polymerization methods, but it is impossible to control the molecular weight, and the molecular weight distribution is wide and used. There is a problem that possible solvents and monomers are limited.
또한, 입도분포가 다분산성이기 때문에 칼럼 충진제로 사용할 경우 미세입자로 인한 칼럼 효율의 저하, 압력강하 및 수명단축 등의 단점과 생의약 분야에서 효소 및 항체의 고정화제로 사용할 때 재현성이 떨어지는 단점이 있다.In addition, since the particle size distribution is polydisperse, when used as a column filler, there are disadvantages such as deterioration of column efficiency, pressure drop, and shortening of life due to fine particles, and poor reproducibility when used as an immobilizing agent for enzymes and antibodies in the biomedical field. .
이와 같이 단분산성의 중합체 입자를 얻기 위하여 여러 방법들이 제시되었지만, 수 ㎛에서 수십 ㎛ 이상의 균일한 중합체 입자를 얻기가 어렵고, 단량체와 용매의 선택에 제약이 따른다.Although several methods have been proposed for obtaining monodisperse polymer particles as described above, it is difficult to obtain uniform polymer particles of several micrometers to tens of micrometers or more, and the selection of monomers and solvents is limited.
그러므로 수 ㎛에서 수십 ㎛ 이상의 단분산성 다공의 중합체 입자를 합성하기 위해서는 유화중합법에 의하여 합성된 ㎛ 크기의 균일한 시이드 입자를 적절한 용매를 사용하여 요구되는 크기까지 일정한 크기로 입자들을 성장시키는 것이 요구된다.Therefore, in order to synthesize monodisperse porous polymer particles of several micrometers to several tens of micrometers or more, it is necessary to grow uniform seed particles having a size of μm synthesized by emulsion polymerization to a required size using a suitable solvent to a desired size. Required.
이에 본 발명은 위와 같은 문제점을 해결하여 입자의 크기를 정확히 조절할 수 있고, 입자의 크기가 균일한 다공구조를 갖는 중합체 입자의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a method for preparing a polymer particle having a porous structure in which the size of the particle can be precisely adjusted by solving the above problems and the particle size is uniform.
도 1은 제조예 1에서 만들어진 중합체를 전자현미경으로 나타낸 사진이다.1 is a photograph showing the polymer produced in Preparation Example 1 by an electron microscope.
도 2는 제조예 2에서 만들어진 중합체를 전자현미경으로 나타낸 사진이다.2 is a photograph showing an electron microscope of the polymer prepared in Preparation Example 2. FIG.
도 3은 제조예 3에서 만들어진 중합체를 전자현미경으로 나타낸 사진이다.3 is a photograph showing an electron microscope of the polymer prepared in Preparation Example 3. FIG.
도 4는 제조예 4에서 만들어진 중합체를 전자현미경으로 나타낸 사진이다.4 is a photograph showing an electron microscope of the polymer prepared in Preparation Example 4. FIG.
도 5는 실시예 1에서 제조된 중합체 입자를 전자현미경으로 나타낸 사진이다.5 is a photograph showing an electron microscope of the polymer particles prepared in Example 1.
도 6는 실시예 6에서 제조된 중합체 입자를 전자현미경으로 나타낸 사진이다.6 is a photograph showing an electron microscope of the polymer particles prepared in Example 6.
도 7은 실시예 11에서 제조된 중합체 입자를 전자현미경으로 나타낸 사진이다.Figure 7 is a photograph showing the electron micrograph of the polymer particles prepared in Example 11.
본 발명은 소수 및 친수성의 모노비닐 단량체, 분산안정제, 유상의 개시제, 가교제로서 디비닐 단량체, 희석제, 증류수 및 시이드 중합체 등의 매개물을 초음파 발생장치를 사용하여 용액 속에 균일하게 분산시켜 혼합하는 단계,The present invention is to uniformly disperse and mix the media such as divinyl monomer, diluent, distilled water and the seed polymer as hydrophobic and hydrophilic monovinyl monomer, dispersion stabilizer, oil phase initiator, crosslinking agent in a solution using an ultrasonic wave generator ,
분산안정제에 의하여 상기 용액 속에 균일하게 분산되어 있는 시이드 중합체를 희석제와 단량체에 의하여 일정한 크기로 팽윤시켜, 팽윤된 시이드 속으로 상기 매개물들을 녹이는 단계,Swelling the seed polymer uniformly dispersed in the solution by a dispersion stabilizer to a predetermined size with a diluent and a monomer to dissolve the media into the swollen seed,
상기 용액을 반응이 일어날 수 있는 온도로 가열하여 중합반응을 일으키는 단계, 및Heating the solution to a temperature at which the reaction can occur to cause a polymerization reaction, and
중합반응이 완결되고 미반응 단량체, 시이드, 희석제 및 분산안정제 등을 제거하기 위하여 유기용매와 물을 사용하여 세척하는 단계로 이루어진 입자크기가 균일한 다공성 중합체 입자의 제조방법이다.It is a method for producing porous polymer particles having a uniform particle size consisting of washing with an organic solvent and water to complete the polymerization reaction and remove unreacted monomers, seeds, diluents and dispersion stabilizers.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
상기 본 발명의 제조방법은 유화중합법으로 합성된 단분산성의 선상 또는 가교된 시이드 중합체를 사용하여, 이 시이드를 단량체와 희석제에 의해 팽윤시켜 입자크기가 증대되고 입도분포가 균일한 중합체 입자를 합성하는 중합법이다.The production method of the present invention uses a monodisperse linear or crosslinked seed polymer synthesized by emulsion polymerization, and swells the seed with a monomer and a diluent to increase particle size and uniform particle size distribution. It is a polymerization method which synthesize | combines.
시이드 중합체를 단량체와 희석제를 통해 팽윤시키는 것은 시이드 중합체는 물에 거의 녹지 않는 유용성 물질이고, 희석제도 유기용매이므로 물과 혼합되지 않는다. 따라서, 희석제는 시이드 중합체 및 단량체를 용해시킬 수 있다. 부틸메타크릴레이트와 디비닐벤젠과 같은 소수성의 단량체는 상호간 잘 섞이는 유기용매에 의하여 팽윤된 시이드 속으로 녹아들어가 시이드를 팽윤시킨다. 이와 같이 시이드가 팽윤되는 정도는 첨가되는 희석제와 단량체의 양에 따라 결정된다.Swelling the seed polymer through monomers and diluents is a useful material that is almost insoluble in water, and since the diluent is an organic solvent, it is not mixed with water. Thus, the diluent can dissolve the seed polymer and monomer. Hydrophobic monomers, such as butyl methacrylate and divinylbenzene, melt into the swollen seeds by mixing well with each other to swell the seeds. The extent to which the seed swells is thus determined by the amount of diluent and monomer added.
그러나, 아크릴로니트릴 및 비닐피리딘과 같은 친수성의 단량체는 염화나트륨과 같은 전해질을 사용하여 단량체의 물에 대한 용해도를 감소시키는 방법을 사용하여 이용할 수 있다. 단량체들이 물에 녹아서 중합이 이루어지면 구형의 입자를 얻을 수 없고 덩어리 형태로 얻어지기 때문에 단량체의 용해도를 낮추는 것은 중요하다.However, hydrophilic monomers such as acrylonitrile and vinylpyridine can be used using a method of reducing the solubility of the monomers in water using an electrolyte such as sodium chloride. It is important to reduce the solubility of the monomer because the monomers are dissolved in water and polymerized so that spherical particles are not obtained but are obtained in the form of agglomerates.
상기, 제조방법으로 합성된 중합체 입자의 형태는 중심-쉘(core-shell)형이나 비표면적이 큰 다공성의 중합체 입자로 얻을 수 있으며, 입도분포가 단분산성이므로 입자크기에 따른 분류 작업이 필요없기 때문에 경제적이고 실험에 대한 재현성이 좋다.The polymer particles synthesized by the manufacturing method may be obtained in the form of core-shell type or porous polymer particles having a large specific surface area, and the particle size distribution is monodisperse, thus eliminating the necessity of classification according to particle size. Because of the economic and reproducibility of the experiment.
상기에서, 시이드 중합체는 단량체에 대해 팽윤성을 가지며, 입자크기가 0.1㎛ 내지 10㎛ 정도되는 것이 바람직하다.In the above, the seed polymer is swellable with respect to the monomer, and the particle size is preferably about 0.1㎛ to 10㎛.
상기에서, 매개물로 사용된 모노비닐 단량체로는 스티렌, 메틸메타크릴레이트, 에틸메타크릴레이트, 부틸메타크릴레이트, 글리시딜메타크릴레이트, 2-에틸헥실아크릴레이트, 2-에틸헥실메타크릴레이트, 라우릴아크릴레이트, 라우릴메타크릴레이트, 스테아릴아크릴레이트, 스테아릴메타크릴레이트, 부타디엔, 메틸아크릴레이트, 에틸아크릴레이트, 글리시딜아크릴레이트, 부틸아크릴레이트, 비닐아세테이트, 비닐피리딘, 비닐클로리드, 아크릴산, 아크릴아미드 또는 아크릴로니트릴 등의 친수성 및 소수성의 특성을 갖는 비닐계 단량체를 포함할 수 있다.In the above, the monovinyl monomer used as a medium is styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate , Lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, butadiene, methyl acrylate, ethyl acrylate, glycidyl acrylate, butyl acrylate, vinyl acetate, vinyl pyridine, vinyl And vinyl monomers having hydrophilic and hydrophobic properties such as chloride, acrylic acid, acrylamide, or acrylonitrile.
상기 모노비닐 단량체는 0.01 내지 50중량％의 범위내에서 첨가된다.The monovinyl monomer is added in the range of 0.01 to 50% by weight.
또 다른 매개물로서, 가교제인 디비닐 단량체로는 디비닐벤젠, 에틸렌글리콜디메타크릴레이트, 메틸렌비스아크릴아미드, 메틸렌비스메타크릴아미드, 디비닐메타크릴레이트, 디비닐아크릴레이트, 에틸렌글리콜디비닐에테르, 무수아크릴산 또는 무수메타크릴산을 포함할 수 있다.As another medium, the divinyl monomer as a crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, methylenebisacrylamide, methylenebismethacrylamide, divinyl methacrylate, divinyl acrylate, ethylene glycol divinyl ether , Acrylic acid anhydride or methacrylic anhydride.
중합개시제로는 아조비스이소부티로니트릴, 아조비스디메틸발레로니트릴과 같은 아조화합물 또는 큐멘히드로퍼옥사이드, t-부틸히드로퍼옥사이드, 디큐밀퍼옥사이드, 디-t-부틸퍼옥사이드, 벤조일퍼옥사이드 및 라우로인퍼옥사이드 등과 같은 과산화물을 포함할 수 있다.Polymerization initiators include azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile or cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide and Peroxides such as lauroin peroxide and the like.
분산안정제는 용매중 시이드 중합체 입자의 분산성을 향상시키기 위해 사용되는 것으로 비이온성 계면활성제, 음이온성 계면활성제, 양이온성 계면활성제 또는 양쪽성 계면활성제에서 선택된다.Dispersion stabilizers are used to improve the dispersibility of the seed polymer particles in the solvent and are selected from nonionic surfactants, anionic surfactants, cationic surfactants or amphoteric surfactants.
희석제로는 톨루엔, 크실렌, 사염화탄소, 이소아밀 알콜 또는 시클로헥산 등비극성 용매가 사용된다.As the diluent, nonpolar solvents such as toluene, xylene, carbon tetrachloride, isoamyl alcohol or cyclohexane are used.
시이드 중합체로는 스티렌, α-메틸스티렌, 메틸메타크릴레이트, 에틸메타크릴레이트, 부틸메타크릴레이트, 글리시딜메타크릴레이트, 히드록시에틸아크릴레이트, 2-에틸헥실아크릴레이트, 2-에틸헥실메타크릴레이트, 라우릴아크릴레이트, 라우릴메타크릴레이트, 스테아릴아크릴레이트, 스테아릴메타크릴레이트, 메틸아크릴레이트, 에틸아크릴레이트, 글리시딜아크릴레이트, 부틸아크릴레이트, 비닐아세테이트, 비닐피리딘, 비닐클로라이드, 아크릴산, 아크릴아미드 또는 아크릴로니트릴 등이 사용된다.Seed polymers include styrene, α-methylstyrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate, 2-ethyl Hexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, glycidyl acrylate, butyl acrylate, vinyl acetate, vinyl pyridine , Vinyl chloride, acrylic acid, acrylamide or acrylonitrile and the like are used.
상기, 시이드 중합체는 0.001 내지 50중량％ 범위에서 첨가된다.The seed polymer is added in the range of 0.001 to 50% by weight.
또한, 시이드 중합체에 대한 모노비닐 단량체의 중량비는 1.0 내지 100의 범위인 것이 바람직하다.In addition, the weight ratio of the monovinyl monomer to the seed polymer is preferably in the range of 1.0 to 100.
또한, 모노비닐 단량체에 대한 디비닐 단량체의 중량비는 0.01 내지 10의 범위인 것이 바람직하다.In addition, the weight ratio of the divinyl monomer to the monovinyl monomer is preferably in the range of 0.01 to 10.
또한, 모노비닐 단량체에 대한 희석제의 중량비는 0.1 내지 10의 범위인 것이 바람직하다.In addition, the weight ratio of the diluent to the monovinyl monomer is preferably in the range of 0.1 to 10.
또한 시이드 중합은 팽윤조건, 단량체의 종류, 양 및 가교제의 농도 등에 따라 용도에 맞는 입자크기와 특성을 갖는 중합체 입자를 얻을 수 있으며, 표면적이 증대된 다공구조의 중합체 입자를 합성할 수 있어 많은 응용성이 기대된다.In addition, the seed polymerization can obtain polymer particles having particle size and properties suitable for the application depending on the swelling conditions, the type, amount of the monomer and the concentration of the crosslinking agent, and it is possible to synthesize porous polymer particles having an increased surface area. Applicability is expected.
이하, 실시예에 의거 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to Examples.
제조예 1Preparation Example 1
교반기, 환류냉각기, 질소가스 유입장치, 온도계가 부착된 4구 플라스크 속에 폴리비닐피롤리돈 5.0g, 소디움디옥틸설포석시네이트 1.0g을 에탄올/증류수 혼합용액 200㎖에 녹인 다음, 스티렌 30.0g과 아조비스이소부티로니트릴 0.15g을 첨가하고 50℃ 내지 70℃에서 200rpm 내지 400rpm으로 4시간 동안 반응시키면 스티렌 중합체가 생성된다.Dissolve 5.0 g of polyvinylpyrrolidone and 1.0 g of sodium dioctylsulfosuccinate in 200 ml of a mixture of ethanol / distilled water in a four-necked flask equipped with a stirrer, reflux cooler, nitrogen gas inlet, and a thermometer. Styrene polymer is produced by adding 0.15 g of azobisisobutyronitrile and reacting at 200 to 400 rpm for 4 hours at 50 to 70 캜.
상기 반응으로 얻어진 중합체를 원심분리하고 메탄올로 수회 세척한 다음 건조시켜 입자크기가 균일한 30g의 미세한 중합체 입자를 얻었다. 전자현미경으로 관찰한 중합체의 형태는 도 1에 나타낸 것과 같이 입자의 크기는 1.0㎛으로 입도분포가 매우 좁은 단분산성의 형태를 갖는 것을 알 수 있었다(도 1).The polymer obtained by the reaction was centrifuged, washed several times with methanol and dried to obtain 30 g of fine polymer particles having a uniform particle size. As shown in FIG. 1, the polymer was observed under an electron microscope, and the particle size was 1.0 μm, indicating that the particle size distribution had a very narrow monodisperse form (FIG. 1).
제조예 2Preparation Example 2
교반기, 환류냉각기, 질소가스 유입장치, 온도계가 부착된 4구 플라스크속에 폴리비닐피롤리돈 3.0g, 소디움디옥틸설포석시네이트 1.0g을 에탄올/증류수 혼합용액 200㎖에 녹인 다음, 스티렌 30.0g과 아조비스이소부티로니트릴 0.15g을 첨가하고 50 내지 70℃에서 200 내지 400rpm으로 8시간 동안 반응시키면 스티렌 중합체가 생성된다.In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen gas inlet, and a thermometer, 3.0 g of polyvinylpyrrolidone and 1.0 g of sodium dioctylsulfosuccinate were dissolved in 200 ml of an ethanol / distilled water mixture, followed by 30.0 g of styrene. Styrene polymer is produced by adding 0.15 g of azobisisobutyronitrile and reacting at 200 to 400 rpm for 8 hours at 50 to 70 캜.
상기 반응으로 얻어진 중합체를 원심분리하고 메탄올로 수회 세척한 다음 건조시켜 입자크기가 균일한 30g의 미세한 중합체 입자를 얻었다. 전자현미경으로 관찰한 중합체의 형태는 도 2에 나타낸 바와 같이 입자의 크기는 1.5㎛이고 입도분포가 매우 좁은 단분산성의 형태를 갖는 것을 알 수 있었다(도 2).The polymer obtained by the reaction was centrifuged, washed several times with methanol and dried to obtain 30 g of fine polymer particles having a uniform particle size. As shown in FIG. 2, the shape of the polymer observed under an electron microscope was found to have a monodisperse form with a particle size of 1.5 μm and a very small particle size distribution (FIG. 2).
제조예 3Preparation Example 3
교반기, 환류냉각기, 질소가스 유입장치, 온도계가 부착된 4구 플라스크 속에 폴리비닐피롤리돈 2.0g, 소디움디옥틸설포석시네이트 1.0g을 에탄올 200㎖에 녹인 다음, 스티렌 30.0g과 아조비스이소부티로니트릴 0.15g을 첨가하고 50℃ 내지 70℃에서 200㎛ 내지 400rpm으로 4시간 동안 반응시키면 스티렌 중합체가 생성된다.Dissolve 2.0 g of polyvinylpyrrolidone and 1.0 g of sodium dioctylsulfosuccinate in 200 ml of ethanol in a four-necked flask equipped with a stirrer, reflux cooler, nitrogen gas inlet, and a thermometer, and then 30.0 g of styrene and azobisisobuty. 0.15 g of ronitrile was added and reacted for 4 hours at 200 to 400 rpm at 50 ° C to 70 ° C to form a styrene polymer.
상기 반응으로 얻어진 중합체를 원심분리하고 메탄올로 수회 세척한 다음 건조시켜 입자크기가 균일한 30g의 미세한 중합체 입자를 얻었다. 전자현미경으로 관찰한 중합체의 형태는 도 4에 나타낸 바와 같이 입자의 크기는 2.0㎛이고 입도분포가 매우 좁은 단분산성의 형태를 갖는 것을 알 수 있었다(도 3).The polymer obtained by the reaction was centrifuged, washed several times with methanol and dried to obtain 30 g of fine polymer particles having a uniform particle size. As shown in FIG. 4, the shape of the polymer observed under an electron microscope showed that the particle size was 2.0 μm and the particle size distribution had a very narrow monodisperse form (FIG. 3).
제조예 4Preparation Example 4
교반기, 환류냉각기, 질소가스 유입장치, 온도계가 부착된 4구 플라스크 속에 폴리비닐피롤리돈 1.5g, 소디움디옥틸설포석시네이트 1.0g을 에탄올 200㎖에 녹인 다음, 스티렌 30.0g과 아조비스이소부티로니트릴 0.15g을 첨가하고 50℃ 내지 70℃에서 200rpm 내지 400rpm으로 4시간 동안 반응시키면 스티렌 중합체가 생성된다.Dissolve 1.5 g of polyvinylpyrrolidone and 1.0 g of sodium dioctylsulfosuccinate in 200 ml of ethanol in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen gas inlet, and a thermometer, and then 30.0 g of styrene and azobisisobuty. Styrene polymer is produced by adding 0.15 g of ronitrile and reacting at 200 to 400 rpm for 4 hours at 50 to 70 캜.
상기 반응으로 얻어진 중합체를 원심분리하고 메탄올로 수회 세척한 다음 건조시켜 입자크기가 균일한 30g의 미세한 중합체 입자를 얻었다. 전자현미경으로 관찰한 중합체의 형태는 도 4에 나타낸 바와 같이 입자의 크기는 3.5㎛이고 입도분포가 매우 좁은 단분산성의 형태를 갖는 것을 알 수 있었다(도 4).The polymer obtained by the reaction was centrifuged, washed several times with methanol and dried to obtain 30 g of fine polymer particles having a uniform particle size. As shown in FIG. 4, the shape of the polymer observed under an electron microscope showed that the particle size was 3.5 μm and the particle size distribution had a very narrow monodisperse form (FIG. 4).
실시예 1Example 1
제조예 1에서 제조한 폴리스티렌 입자를 1.0 중량% 폴리비닐알콜 수용액에 0.05g/㎖의 농도로 분산시키고 분산된 폴리스티렌 일정량을 메카니컬 교반기, 환류냉각기, 질소가스 유입장치, 온도계가 부착된 4구 플라스크속에 첨가하고 부틸메타크릴레이트, 디비닐벤젠, 2,2'-아조비스디메틸발레로니트릴 및 톨루엔/이소아밀알콜의 혼합용액(유층)과 소디움디옥틸설포석시네이트와 1.0 중량% 폴리비닐알콜 수용액의 혼합용액(수층)을 만든다. 유층의 혼합용액을 수층의 혼합용액에 첨가하고 얼음물로 냉각시키면서 약 1시간 동안 초음파 발생기를 사용하여 백색의 균일한 현탁액이 될 때까지 분산시킨다. 분산된 유적의 형태를 광학현미경으로 관찰하면서 적하깔때기를 사용하여 약 3시간 동안 반응기에 서서히 떨어뜨린다. 반응 혼합물을 200rpm 내지 400rpm으로 교반하면서 24시간 동안 방치하여 일정한 크기로 팽윤된 스티렌 시이드 입자를 광학현미경으로 관찰한 다음 50℃ 내지 70℃에서 4시간 동안 반응시켜 중합체를 얻었다.The polystyrene particles prepared in Preparation Example 1 were dispersed in a 1.0 wt% polyvinyl alcohol solution at a concentration of 0.05 g / ml, and a predetermined amount of polystyrene was dispersed in a four-necked flask equipped with a mechanical stirrer, a reflux cooler, a nitrogen gas inlet device, and a thermometer. Of a mixed solution of butyl methacrylate, divinylbenzene, 2,2'-azobisdimethylvaleronitrile and toluene / isoamyl alcohol (oil layer), sodium dioctylsulfosuccinate and 1.0 wt% polyvinyl alcohol Prepare a mixed solution (aqueous layer). The mixed solution of the oil layer is added to the mixed solution of the aqueous layer and dispersed using an ultrasonic generator for about 1 hour while cooling with ice water until a white uniform suspension is obtained. While observing the shape of the dispersed remains with an optical microscope, the dropping funnel is slowly dropped into the reactor for about 3 hours. The reaction mixture was allowed to stand for 24 hours with stirring at 200 rpm to 400 rpm to observe swelled styrene seed particles with a constant size under an optical microscope, and then reacted for 4 hours at 50 ° C to 70 ° C to obtain a polymer.
상기 반응에 의해 얻어진 중합체를 증류수와 유기용매로 세척한 후 글라스 필터로 여과하고 건조시켜 입자의 형태가 균일하고 입자표면에 다공구조를 가지고 있는 미세한 중합체 입자를 얻었다.The polymer obtained by the above reaction was washed with distilled water and an organic solvent, filtered through a glass filter and dried to obtain fine polymer particles having a uniform particle shape and a porous structure on the particle surface.
상기 중합반응에 있어서 사용된 매개물들의 조성은 표 1에 나타내었으며, 주사전자현미경으로 관찰한 입자의 형태를 도 5에 나타내었다. 도 5에 나타난 결과로부터 알수 있듯이, 본 실험으로 얻어진 중합체 입자는 입자의 크기가 균일하였으며, 입자의 크기는 평균 2.8㎛이고 입자의 표면은 다공구조를 갖는다. (도 5)The composition of the mediators used in the polymerization reaction is shown in Table 1, and the shape of particles observed with a scanning electron microscope is shown in FIG. As can be seen from the results shown in FIG. 5, the polymer particles obtained in this experiment had a uniform particle size, an average particle size of 2.8 μm, and a surface of the particle having a porous structure. (Figure 5)
실시예 2Example 2
실시예 1에서 사용한 중합조건과 동일한 방법을 사용하고 첨가된 단량체/시이드의 중량 비율을 변화시키면서 실험하여 중합체 입자를 얻었다. 그 결과를 표 1-a에 나타냈다.The polymer particles were obtained by experiment using the same method as the polymerization conditions used in Example 1 and changing the weight ratio of the added monomer / side. The results are shown in Table 1-a.
표 1-aTable 1-a
실시예 3Example 3
실시예 1에서 사용한 중합조건과 동일한 방법을 사용하고 첨가된 모노비닐 단량체와 디비닐 단량체의 중량 비율을 변화시키면서 실험하여 중합체 입자를 얻었다. 그 결과를 표 1-b에 나타냈다.Using the same method as the polymerization conditions used in Example 1 and experimenting while changing the weight ratio of the added monovinyl monomer and divinyl monomers to obtain a polymer particle. The results are shown in Table 1-b.
표 1-bTable 1-b
실시예 4Example 4
실시예 1에서 사용한 중합조건과 동일한 방법을 사용하고 첨가된 희석제(유기용매)의 종류를 변화시키면서 실험하여 중합체 입자를 얻었다. 그 결과를 표 1-c에 나타냈다.The polymer particles were obtained by experiment using the same method as the polymerization conditions used in Example 1 and changing the type of the added diluent (organic solvent). The results are shown in Table 1-c.
표 1-cTable 1-c
실시예 5Example 5
실시예 1에서 사용한 중합조건과 동일한 방법을 사용하고 첨가된 단량체/희석제(유기용매)의 중량 비율을 변화시키면서 실험하여 중합체 입자를 얻었다. 그 결과를 표 1-d에 나타냈다.Using the same method as the polymerization conditions used in Example 1 and experimenting while changing the weight ratio of the added monomer / diluent (organic solvent) to obtain a polymer particle. The results are shown in Table 1-d.
표 1-dTable 1-d
실시예 6Example 6
제조예 1에서 제조한 폴리스티렌 입자를 1.0 중량% 폴리비닐알콜(이하, PVA라 함) 수용액에 0.05g/㎖의 농도로 분산시키고 분산된 폴리스티렌 일정량을 교반기, 환류냉각기, 질소가스 유입장치, 온도계가 설치된 4구 플라스크 속에 첨가하고 아크릴로니트릴, 에틸렌글리콜디메타크릴레이트, 2,2'-아조비스디메틸발레로니트릴 및 톨루엔의 혼합용액(유층)과 1.0 중량% 폴리비닐알콜 수용액과 22.0 중량% NaCl 수용액의 혼합용액(수층)을 만든다.The polystyrene particles prepared in Preparation Example 1 were dispersed at a concentration of 0.05 g / ml in an aqueous solution of 1.0% by weight polyvinyl alcohol (hereinafter referred to as PVA), and a predetermined amount of polystyrene was dispersed in a stirrer, a reflux cooler, a nitrogen gas inlet device, and a thermometer. It was added to an installed four-necked flask, and a mixed solution of acrylonitrile, ethylene glycol dimethacrylate, 2,2'-azobisdimethylvaleronitrile and toluene (oil layer), 1.0% by weight polyvinyl alcohol solution and 22.0% by weight NaCl were added. A mixed solution (aqueous layer) of aqueous solution is prepared.
유층의 혼합용액을 수층의 혼합용액에 첨가하고 얼음물로 냉각시키면서 약 1시간 동안 초음파 발생기를 사용하여 백색의 균일한 현탁액이 될 때까지 분산시킨다. 분산된 유적의 형태를 광학현미경으로 관찰하면서 적하깔때기를 사용하여 약 3시간 동안 반응기에 서서히 떨어뜨린다. 반응 혼합물을 200rpm 내지 400rpm으로 교반하면서 24시간 동안 방치하여 일정한 크기로 팽윤된 스티렌 시이드 입자를 광학현미경으로 관찰한 다음 50℃ 내지 70℃에서 4시간 동안 반응시켜 중합체를 얻었다.The mixed solution of the oil layer is added to the mixed solution of the aqueous layer and dispersed using an ultrasonic generator for about 1 hour while cooling with ice water until a white uniform suspension is obtained. While observing the shape of the dispersed remains with an optical microscope, the dropping funnel is slowly dropped into the reactor for about 3 hours. The reaction mixture was allowed to stand for 24 hours with stirring at 200 rpm to 400 rpm to observe swelled styrene seed particles with a constant size under an optical microscope, and then reacted for 4 hours at 50 ° C to 70 ° C to obtain a polymer.
상기 반응에 의해 얻어진 중합체를 증류수와 유기용매로 세척한 후 글라스 필터로 여과하고 건조시켜 입자의 형태가 균일하고 입자표면에 다공구조를 가지고 있는 미세한 중합체 입자를 얻었다.The polymer obtained by the above reaction was washed with distilled water and an organic solvent, filtered through a glass filter and dried to obtain fine polymer particles having a uniform particle shape and a porous structure on the particle surface.
상기 중합반응에 있어서, 용액내의 매개물들의 비율은 표 2에 나타내었으며, 주사전자현미경으로 관찰한 입자의 형태를 도 6에 나타내었다. 도 6에 나타낸 결과로부터 알 수 있듯이, 본 실험으로 얻어진 중합체는 입자의 크기가 균일하였으며, 입자의 크기는 평균 5.2㎛이고, 입자의 표면은 다공구조를 갖는다.[도 6]In the polymerization reaction, the ratio of the mediators in the solution is shown in Table 2, and the shape of the particles observed with the scanning electron microscope is shown in FIG. As can be seen from the results shown in FIG. 6, the polymers obtained in this experiment had uniform particle sizes, an average particle size of 5.2 μm, and the surface of the particles had a porous structure.
실시예 7Example 7
실시예 6에서 사용한 중합조건과 동일한 방법을 사용하고, 첨가된 단량체/시이드의 중량 비율을 변화시키면서 실험하여 중합체 입자를 얻었다. 그 결과를 표 2-a에 나타냈다.Using the same method as the polymerization conditions used in Example 6, experiments were carried out while varying the weight ratio of the added monomer / side to obtain polymer particles. The results are shown in Table 2-a.
표 2-aTable 2-a
실시예 8Example 8
실시예 6에서 사용한 중합조건과 동일한 방법을 사용하고, 첨가된 모노비닐단량체/디비닐 단량체의 중량 비율을 변화시키면서 실험하여 중합체 입자를 얻었다. 그 결과를 표 2-b에 나타냈다.Using the same method as the polymerization conditions used in Example 6, experiments were carried out while varying the weight ratio of the added monovinyl monomer / divinyl monomer to obtain polymer particles. The results are shown in Table 2-b.
표 2-bTable 2-b
실시예 9Example 9
실시예 6에서 사용한 중합조건과 동일한 방법을 사용하고, 첨가된 희석제(유기용매)의 종류를 변화시키면서 실험하여 중합체 입자를 얻었다.The polymer particles were obtained by experimenting using the same method as the polymerization conditions used in Example 6 while changing the type of the added diluent (organic solvent).
표 2-cTable 2-c
실시예 10Example 10
실시예 6에서 사용한 중합조건과 동일한 방법을 사용하고, 첨가된 단량체/희석제(유기용매)의 비율을 변화시키면서 실험하여 중합체 입자를 얻었다.Using the same method as the polymerization conditions used in Example 6, experiments were carried out while varying the ratio of the added monomer / diluent (organic solvent) to obtain polymer particles.
실시예 11Example 11
제조예 1에서 제조한 폴리스티렌 입자를 1.0 중량% 폴리비닐알콜 수용액에 0.05g/㎖의 농도로 분산시키고 분산된 폴리스티렌 일정량을 교반기, 환류냉각기, 질소가스 유입장치, 온도계가 설치된 4구 플라스크속에 첨가하고 4-비닐피리딘, 디비닐벤젠, 2,2'-아조비스디메틸발레로니트릴 및 톨루엔/이소아밀알콜의 혼합용액(유층)을 만들고 소디움디옥틸설포석시네이트, 1.0 중량% 폴리비닐알콜 수용액 및 22.0 중량% NaCl 수용액의 혼합용액(수층)을 만든다.The polystyrene particles prepared in Preparation Example 1 were dispersed in a 1.0 wt% polyvinyl alcohol solution at a concentration of 0.05 g / ml, and a predetermined amount of the dispersed polystyrene was added to a four-necked flask equipped with a stirrer, a reflux cooler, a nitrogen gas inlet apparatus, and a thermometer. A mixed solution (oil layer) of 4-vinylpyridine, divinylbenzene, 2,2'-azobisdimethylvaleronitrile and toluene / isoamyl alcohol was prepared and sodium dioctylsulfosuccinate, 1.0 wt% aqueous polyvinyl alcohol solution and 22.0 A mixed solution (aqueous layer) of a wt.
유층의 혼합용액을 수층의 혼합용액에 첨가하고 얼음물로 냉각시키면서 약 1시간 동안 초음파 발생기를 사용하여 백색의 균일한 현탁액이 될 때까지 분산시킨다. 분산된 유적의 형태를 광학현미경으로 관찰하면서 적하깔때기를 사용하여 약 3시간 동안 반응기에 서서히 떨어뜨린다. 반응 혼합물을 200rpm 내지 400rpm으로 교반하면서 24시간 동안 방치하여 일정한 크기로 팽윤된 스티렌 시이드 입자를 광학현미경으로 관찰한 다음 50℃ 내지 70℃에서 4시간 동안 반응시켜 중합체를 얻었다.The mixed solution of the oil layer is added to the mixed solution of the aqueous layer and dispersed using an ultrasonic generator for about 1 hour while cooling with ice water until a white uniform suspension is obtained. While observing the shape of the dispersed remains with an optical microscope, the dropping funnel is slowly dropped into the reactor for about 3 hours. The reaction mixture was allowed to stand for 24 hours with stirring at 200 rpm to 400 rpm to observe swelled styrene seed particles with a constant size under an optical microscope, and then reacted for 4 hours at 50 ° C to 70 ° C to obtain a polymer.
상기 반응에 의해 얻어진 중합체를 증류수와 유기용매로 세척한 후 글라스 필터로 여과하고 건조시켜 입자의 형태가 균일하고 입자표면에 다공구조를 가지고 있는 미세한 중합체 입자를 얻었다.The polymer obtained by the above reaction was washed with distilled water and an organic solvent, filtered through a glass filter and dried to obtain fine polymer particles having a uniform particle shape and a porous structure on the particle surface.
상기 중합반응에 있어서, 용액내의 매개물들의 비율은 표 3에 나타내었으며, 주사전자현미경으로 관찰한 입자의 형태를 도 7에 나타내었다. 도 7에 나타낸 결과로부터 알 수 있듯이, 본 실험으로 얻어진 중합체는 입자의 크기가 균일하였으며, 입자의 크기는 평균 3.7㎛이고, 입자의 표면은 다공구조를 갖는다.[도 7]In the polymerization reaction, the ratio of the mediators in the solution is shown in Table 3, and the shape of the particles observed by the scanning electron microscope is shown in FIG. As can be seen from the results shown in FIG. 7, the polymers obtained in this experiment had uniform particle sizes, an average particle size of 3.7 μm, and the surface of the particles had a porous structure.
상기 표 1a-d 및 표 2 a-c에 나타난 바와 같이 시이드 중합은 시이드 중합체, 단량체, 희석제 등의 종류 및 양에 따라 용도에 맞는 입자크기와 특성을 갖는 균일한 다공성 중합체 입자를 비교적 간단한 방법에 따라 얻을 수 있다.As shown in Table 1a-d and Table 2 ac, the Seed polymerization is performed in a relatively simple manner by uniform homogeneous polymer particles having particle size and characteristics suitable for the purpose according to the type and amount of the seed polymer, monomer, diluent and the like. You can get along.
이와 같이, 본 발명의 다공성 중합체 입자의 제조방법은 비교적 간단한 방법으로 저렴하게 중합체 입자를 제조할 수 있고, 입자의 표면 특성 및 화학적 변형방법으로 중합체 입자에 치환기를 도입시킴으로서 이온의 흡착능과 선택성을 갖는 중합체 입자를 제조할 수 있다.As described above, the method of preparing the porous polymer particles of the present invention can produce the polymer particles in a relatively simple manner at a low cost, and has the adsorption ability and the selectivity of the ions by introducing substituents into the polymer particles by the surface properties and chemical modification methods of the particles. Polymer particles can be prepared.
또한, 제조된 다공성 중합체 입자는 표면적이 크기 때문에 진단용 의약, 약물전달체, 촉매 및 효소의 담체, 유전자의 분리정제 등에 다양하게 이용되고, 특히 급속한 산업화로 문제가 되고 있는 중금속에 의한 환경오염 방지에 응용할 수 있으므로 공업적인 면에서 가치가 클 것으로 기대된다.In addition, since the prepared porous polymer particles have a large surface area, they are widely used in diagnostic medicines, drug carriers, carriers of catalysts and enzymes, and separation and purification of genes, and are particularly applicable to the prevention of environmental pollution by heavy metals, which is a problem due to rapid industrialization. It is expected to be of great industrial value.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030042409A (en) * | 2001-11-20 | 2003-05-28 | 주식회사 효성 | The Manufacturing Method Of Acryl Globular Corpuscle |
| KR100480336B1 (en) * | 2001-12-27 | 2005-04-06 | 제일모직주식회사 | Monodisperse Polymer Particles Having Full Inter-penetrating Polymer Network Structure and Process for Preparing the Same |
| KR100600470B1 (en) * | 2004-10-26 | 2006-07-13 | 주식회사 선진화학 | Preparing method of porous polymethylmethacrlate |
| KR100942677B1 (en) * | 2007-05-03 | 2010-02-17 | 주식회사 엘지화학 | Washing method of chemically polymerized toner |
| CN115141302A (en) * | 2022-07-11 | 2022-10-04 | 杭州师范大学 | Porous poly 4-vinylpyridine polymer microsphere and preparation method thereof |
| CN115626840A (en) * | 2022-09-08 | 2023-01-20 | 重庆锦弘新材料技术工程有限公司 | Concrete durability protection material for sewage treatment plant and application thereof |
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| KR101191118B1 (en) | 2008-04-11 | 2012-10-15 | 주식회사 엘지화학 | Porous charged particle for image display device and method for manufacturing the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030042409A (en) * | 2001-11-20 | 2003-05-28 | 주식회사 효성 | The Manufacturing Method Of Acryl Globular Corpuscle |
| KR100480336B1 (en) * | 2001-12-27 | 2005-04-06 | 제일모직주식회사 | Monodisperse Polymer Particles Having Full Inter-penetrating Polymer Network Structure and Process for Preparing the Same |
| KR100600470B1 (en) * | 2004-10-26 | 2006-07-13 | 주식회사 선진화학 | Preparing method of porous polymethylmethacrlate |
| KR100942677B1 (en) * | 2007-05-03 | 2010-02-17 | 주식회사 엘지화학 | Washing method of chemically polymerized toner |
| CN115141302A (en) * | 2022-07-11 | 2022-10-04 | 杭州师范大学 | Porous poly 4-vinylpyridine polymer microsphere and preparation method thereof |
| CN115626840A (en) * | 2022-09-08 | 2023-01-20 | 重庆锦弘新材料技术工程有限公司 | Concrete durability protection material for sewage treatment plant and application thereof |
| CN115626840B (en) * | 2022-09-08 | 2024-01-12 | 重庆锦弘新材料技术工程有限公司 | Concrete durability protection material for sewage treatment plant and application thereof |
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